KR100973109B1 - Photosensitive composition - Google Patents

Abstract

It provides a highly sensitive photosensitive composition.

In the photosensitive composition containing a photopolymerizable compound and a photoinitiator, the said photoinitiator has a skeleton represented by Formula (1), and the compound whose absorbance in 365 nm is 0.3 or more is used.

(In Formula (1), A, B and G are monovalent organic groups, and E is a conjugated double bond cyclic group which may have a substituent.)

Photosensitivity, photopolymerization, photoinitiator, absorbance, conjugated double bond

Description

Photosensitive composition {PHOTOSENSITIVE COMPOSITION}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a photosensitive composition containing a photopolymerization initiator, and in particular, a photosensitive composition used for forming a color filter, a black matrix, a spacer, and the like in a liquid crystal display. It is about.

The photosensitive composition contains a photopolymerizable compound and a photopolymerization initiator and is cured by irradiating light such as ultraviolet rays. Since this photosensitive composition hardens the part which irradiated light, the pattern of a desired shape is obtained, and it has been used for various uses, such as a printing plate and a photoresist.

In particular, the black matrix in the liquid crystal display device is formed of a photosensitive composition containing a light shielding agent, but due to the presence of the light blocking agent, there is a possibility that the light reaching the deep portion of the film formed of the photosensitive composition is reduced, resulting in insufficient photocuring of the photosensitive composition. There is this.

In the said photosensitive composition, the performance of a photoinitiator becomes an important factor in improving the sensitivity of a photosensitive composition. As such a photoinitiator, the oxime system photoinitiator is developed. (For example, refer patent documents 1-6 etc.).

Patent Document 1: Japanese Patent Publication No. 2004-534797

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-359639

Patent Document 3: Japanese Patent Laid-Open No. 2005-220097

Patent Document 4: Japanese Patent Application Laid-Open No. 2006-160634

Patent Document 5: Japanese Patent Publication No. 2006-516246

Patent Document 6: International Publication No. 2006/018405 Pamphlet

However, new high sensitivity is also required in the said photosensitive composition.

This invention is made | formed in view of the said subject, and an object of this invention is to provide a more sensitive photosensitive composition.

The photosensitive composition of this invention contains a photopolymerizable compound and a photoinitiator,

The photoinitiator contains a compound having a skeleton represented by the formula (1).

(In Formula (1), A, B and G are monovalent organic groups, and E is a conjugated double bond cyclic group which may have a substituent.)

As mentioned above, the sensitivity of the photosensitive composition can be improved by using the photoinitiator which has a specific structure and whose light absorbency in 365 nm is 0.3 or more.

According to this invention, since the photoinitiator with high sensitivity is used, a more sensitive photosensitive composition can be provided.

The photosensitive composition of this invention contains a photopolymerizable compound and a photoinitiator.

The said photoinitiator has a skeleton represented by Formula (1), and contains the compound whose absorbance in 365 nm is 0.3 or more.

(In Formula (1), A, B and G are monovalent organic groups, and E is a conjugated double bond cyclic group which may have a substituent.)

In addition, this absorbance was measured with the slit width 2.0 and the sampling pitch 0.5 by diluting the target initiator to 0.0017% with the organic solvent PGME using the absorbance photometer UV3100 by Shimadzu Corporation.

In the said photosensitive composition, the sensitivity with respect to the light of the specific wavelength irradiated is calculated | required. In general, light including a wavelength of 365 nm is used, and particularly, a high sensitivity to light of 365 nm is required. Also in the compound represented by the said Formula (1), the sensitivity of the photosensitive composition can be improved by using the compound whose light absorbency in 365 nm is 0.3 or more. In particular, in the oxime compound which has a carbazole group as represented by said Formula (1), the effect of a sensitivity improvement is remarkable. Moreover, it is preferable that it is 0.4 or more, and, as for the absorbance in said 365 nm, it is more preferable that it is 0.5 or more.

A, G is preferably a group represented by -R ¹ , -OR ¹ , -COR ¹ , -SR ¹ , or -NR ¹ R ² . Moreover, it is preferable that B is -R <^1> , -OR <^1> , -COR <^1> , -SR <^1> , -CONR <^1> R <^2>, or -CN. R ¹ and R ² each independently represent an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, of which an alkyl group and an aralkyl group The alkylene moiety of may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond, and R ¹ and R ² may be combined to form a ring.

As an alkyl group represented by R <^1> and R <^2> , a C1-C20 thing is preferable and a C1-C5 thing is more preferable. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, third butyl group, amyl group, isoamyl group, third amyl group and hexyl group Linear or branched saturated hydrocarbon groups such as heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, third octyl group, nonyl group, isononyl group, decyl group and isodecyl group; And linear or branched unsaturated hydrocarbon groups such as vinyl group, allyl group, butenyl group, ethynyl group and propynyl group. Moreover, you may have a substituent. For example, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group, the 2- (benzoxazol 2-yl) ethenyl group etc. are mentioned. Among them, A is preferably a methyl group.

As an aryl group represented by R <^1> and R <^2> , a C6-C20 thing is preferable and a C6-C10 thing is more preferable. Moreover, you may contain an unsaturated bond. For example, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, etc. are mentioned.

As an aralkyl group represented by R <^1> and R <^2> , a C7-C20 thing is preferable and a C7-C12 thing is more preferable. Moreover, you may contain an unsaturated bond. For example, a benzyl group, the (alpha)-methyl benzyl group, the (alpha), the (alpha)-dimethyl benzyl group, the phenyl ethyl group, the phenylethenyl group, etc. are mentioned.

As the heterocyclic group represented by R ¹ and R ² , at least five membered rings including at least one atom of a nitrogen atom (N), a sulfur atom (S) and an oxygen atom (O), preferably 5 to 5 atoms. 7-membered ring heterocyclic group is mentioned. Condensed ring may be contained in this heterocyclic group, For example, a pyridyl group, a pyrimidyl group, a furyl group, a thiophenyl group, etc. are mentioned.

These R ¹ and R ² may be substituted with a halogen atom. For example, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a chlorophenyl group, a chlorobenzyl group, etc. are mentioned.

Moreover, the alkylene part of the alkyl group and the aralkyl group of these R <^1> and R <^2> may be interrupted by an unsaturated bond, an ether bond, a thioether bond, and an ester bond.

Moreover, as a ring which R <^1> and R <^2> becomes one and can form, a heterocyclic ring is mentioned. As this heterocycle, the 5-membered ring or more, preferably the 5-7 membered heterocyclic group containing at least 1 atom of a nitrogen atom (N), a sulfur atom (S), and an oxygen atom (O) is mentioned. Condensed ring may be contained in this heterocyclic group, For example, a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, etc. are mentioned.

E is a conjugated double bond cyclic group which may have a substituent. As this conjugated double bond cyclic group, the aromatic ring or the heterocyclic ring which has N atom, S atom, and O atom in a ring is mentioned. As this aromatic ring, a phenyl group, a naphthyl group, an anthryl group, etc. are mentioned, for example. As a heterocyclic ring, For example, nitrogen containing 5-membered ring groups, such as a pyrrole group, an imidazolyl group, a pyrazolyl group; Nitrogens, such as a pyridyl group, a pyrazinyl group, a pyrimidyl group, and a pyridazinyl group Containing 6-membered ring group; nitrogen-sulfur-containing groups such as thiazolyl group and isothiazolyl group; nitrogen-oxygen-containing groups such as oxazolyl group and isoxazolyl group; furyl group and pyranyl group Oxygen containing organics, such as; Thienyl group, Sulfur containing groups, such as a thiopyranyl group, etc. are mentioned.

Examples of the substituent in E include -NO ₂ , -CN, -SO ₂ R ³ , -COR ³ , -NR ⁴ R ⁵ , and -R ⁶ .

R <^3> respectively independently represents an alkyl group, These may be substituted by the halogen atom, Among these, the alkylene part of an alkyl group may be interrupted by an ether bond, a thioether bond, and an ester bond. It is preferable that the alkyl group in said R <^3> is C1-C5, for example, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, etc. are mentioned.

R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and these may be substituted with halogen atoms, among which the alkylene portion of the alkyl group and the alkoxy group is interrupted by an ether bond, a thioether bond, or an ester bond ^May be sufficient, and R <^4> and R <^5> may be united, and may form the ring. It is preferable that the alkyl group or the alkoxy group in said R <^4> and R <^5> is C1-C5, For example, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, a methoxy group, an ethoxy group And propoxy groups.

R ⁶ is an alkyl group, part or all of which is substituted with a halogen atom. As an alkyl group in said R <^6> , a C1-C5 thing is preferable, For example, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, etc. are mentioned.

The compound represented by the formula (1) preferably has a bond length (bond length between α-β) of an N atom represented by α and an O atom represented by β, and more preferably 1.360 GPa or more. Do. When the bond length between α-β is 1.360 kPa or more, the sensitivity of the photosensitive composition of the present invention can be improved.

In addition, the compound represented by the formula (1) preferably has a bond order (bond order between α-β) of the N atom represented by α and the O atom represented by β, more preferably 0.965 or less. . When the bond order between α-β is 0.965 or less, the sensitivity of the photosensitive composition of the present invention can be improved.

In addition, the said bond length and the bond order are the values computed by MOPAC using PM5 parameter using molecular modeling software "CAChe Work System® Prosersion 6.1.12.33" (Fujitsu Corporation).

The bond length and the bond order between the?-? Are remarkable, and are greatly changed by the kind of E above which the distance between the atoms of the? And? Atoms is far from each other. That is, it is guessed that the bond length and bond order between (alpha)-(beta) change with this kind of E, and also the sensitivity of the photosensitive composition of this invention is improved.

As a conjugated double bond cyclic group in this E, it is preferable that it is a heterocyclic ring, and the cyclic group which has N atom in a ring is more preferable. As a cyclic group which has N atom in a ring, a nitrogen containing 5-membered ring group and a nitrogen containing 6-membered ring group are preferable, and a nitrogen containing 5-membered ring group is especially preferable. As this nitrogen-containing 5-membered ring group, a pyrrole group is preferable.

Moreover, it is preferable to have N atom as a substituent in said E, and the substituent which is couple | bonded with the ring of a conjugated double bond cyclic group directly is more preferable. Examples of the substituent directly bonded to the ring of the conjugated double bond cyclic group include the above-NR ⁴ R ⁵ , and an amino group, a morpholino group, and the like are particularly preferable.

Moreover, you may use a photoinitiator combining various types of the compound represented by said formula (1), and another photoinitiator. As such another photoinitiator, acetophenone, such as acetophenone, 2, 2- diethoxy acetophenone, p-dimethyl acetophenone, p-dimethylamino propiophenone, dichloro acetophenone, trichloro acetophenone, and p-tert- butyl acetophenone, etc. Benzophenones such as phenones, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, Benzoin ethers such as benzoin isobutyl ether, benzyl dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene and 2- Sulfur compounds such as isopropyl thioxanthene, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone and azobisiso Butyronitrile, benzoylperoxide, Organic peroxides such as menperoxide, thiol compounds such as 2-mercaptobenzoimidal, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and 2- (o-chlorophenyl) -4 , Imidazolyl compounds such as 5-di (m-methoxyphenyl) -imidazolyl dimer, triazine compounds such as p-methoxytriazine, and 2, 4, 6- Tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2 -To [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Tenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n- Triazine compound which has halomethyl group, such as butoxyphenyl) -4 and 6-bis (trichloromethyl) -s-triazine, 2-benzyl 2- dimethylamino-1- (4- And aminoketone compounds such as morpholinophenyl) -butan-1-one.

It is preferable that it is 0.1-50 mass parts with respect to a total of 100 mass parts of solid content, and, as for the said photoinitiator, it is more preferable that it is 1-45 mass parts.

In addition, the said solid content is all the components except a solvent in the photosensitive composition of this invention.

As a photopolymerizable compound, the compound which has ethylene (ethylene) double bond is preferable, Specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, Acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl methacrylate, benzyl arc Ethylene, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetra Ethylene Glycol Dimethacrylate, Butylene Glycol Dimethacrylate, Propylene Glycol Diacrylate, Propylene Glycol Dimethacrylate, Trimethylol Propane Triacrylate, Trimethylol Propane Trimethacrylate, Tetramethylol Propane Tetraacrylate , Tetramethylol propane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate (PTA), pentaerythritol tetramethacrylate, dipenta Rithritol pentaacrylate, dipentaerythritol Pentamethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, cardo Monomers and oligomers such as epoxy diacrylate; polyester (meth) obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensation of polyhydric alcohols with monobasic or polybasic acids Polyurethane (meth) acrylate obtained by reacting a acrylate, a compound having a polyol group and two isocyanate groups, and then reacting (meth) acrylic acid; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin , Phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid poly Epoxy (meth) obtained by reacting epoxy resins such as glycidyl esters, polyol polyglycidyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, and dihydroxybenzene type epoxy resins with (meth) acrylic acid An acrylate resin etc. are mentioned. Moreover, the resin which made polybasic acid anhydride react with the said epoxy (meth) acrylate resin can also be used preferably.

It is preferable that the said photopolymerizable compound combines the said monomer and resin which has an ethylenic double bond. As this monomer, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimetha Acrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, tetramethylol propane tetraacrylate, tetramethylol Propane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, di Pentaerythritol pentamethacrylate Ditrate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, cardoepoxy diacrylate Polyfunctional monomers, such as a rate, are preferable.

As said photopolymerizable compound, it is preferable to contain resin obtained by making the reaction material of an epoxy compound and an unsaturated group containing carboxylic acid further react with polybasic acid anhydride. Especially, the compound represented by following formula (a1) is preferable. The compound represented by a formula (a1) is a preferable compound by the point which is itself high in photocurability.

Here, X of the compound represented by Formula (a1) is group represented by Formula (a2).

The groups represented by R ^1a each independently represent a hydrogen atom, a hydrocarbon group of 1 to 6 carbon atoms and a halogen atom, and R ^2a each independently represents a hydrogen atom or a methyl group, and W represents a single bond or the following formula (a3) Represents a group represented by

Y is a residue except the acid anhydride group of dicarboxylic anhydride, Z is a residue except the acid anhydride group of tetracarboxylic dianhydride, and m is an integer of 0-20.)

Moreover, as said Y, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, The residue remove | excluding the carboxylic anhydride group (-CO-O-CO-) from the dicarboxylic anhydride called methyltetrahydro phthalic anhydride and glutaric anhydride is mentioned.

Moreover, as said Z, tetracarboxyl, such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, and a biphenyl ether tetracarboxylic dianhydride, for example. And residues excluding two carboxylic acid anhydride groups from tetracarboxylic dianhydride.

The acid value of the resin having an ethylenic double bond is preferably 10 mg KOH / g or more and 150 mg KOH / g or less, more preferably 70 mg KOH / g or more and 110 mg KOH / g or less in the resin solid content. By setting the acid value of the resin to 10 mg KOH / g or more, sufficient solubility in the developer is obtained, and by setting the acid value to 150 mg KOH / g or less, sufficient curability can be obtained and the surface property can be improved.

Moreover, it is preferable that the weight average molecular weights of resin which has an ethylenic double bond are 1000 or more and 40000 or less, More preferably, they are 2000 or more and 30000 or less. By setting the weight average molecular weight to 1000 or more, heat resistance and film strength can be improved. Moreover, sufficient solubility with respect to a developing solution can be obtained by setting it as 40000 or less.

It is preferable that the said photopolymerizable compound is contained in 50-99.9 mass parts with respect to 100 mass parts in total of solid content. When the content is 50 parts by mass or more, sufficient heat resistance and chemical resistance can be expected.

The said photopolymerizable compound may contain the coloring agent. As the colorant, for example, a compound classified as a pigment in a color index (CI; issued by The Society Society of Dyers and Colourists), and specifically the following color index (CI) number There is a thing attached. This coloring agent may be used independently, and in order to adjust color tone, you may mix and use 2 or more types.

CI pigment yellow 1 (hereinafter, "CI pigment yellow" is the same, so only numbers are listed.), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

CI pigment orange 1 (hereinafter "CI pigment orange" is the same, so only numbers are listed.), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;

C. I. pigment violet 1 (hereinafter, "C. I. pigment violet" is the same, so only numbers are listed.), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

CI pigment red 1 (hereinafter, "CI pigment red" is the same, so only numbers are listed.), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

CI pigment blue 1 (hereinafter "CI pigment blue" is the same, so only number is listed.), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;

C. I. pigment green 7, C. I. pigment green 36, C. I. pigment green 37;

C. I. pigment brown 23, C. I. pigment brown 25, C. I. pigment brown 26, C. I. pigment brown 28;

C. I. Pigment Black 1, Pigment Black 7.

In addition, when forming a black matrix, a light shielding material is used as a coloring agent. The light shielding material is not particularly limited as long as it has a sufficient light shielding rate when the light shielding layer is used, and for example, a black pigment may be mentioned. Carbon black, titanium black, perylene black, etc. are mentioned as this black pigment.

As the light shielding material, it is preferable to use carbon black or titanium black. In addition, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, Al, etc. Inorganic pigments such as various metal oxides, complex oxides, metal sulfides, metal lead sulfates, or metal carbonates.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black and lamp black can be used, but in particular, the channel black has excellent light shielding properties. It can use preferably. Moreover, resin coated carbon black can also be used. Specifically, a resin-coated carbon black obtained by mixing a carbon black with a resin having reactivity with a carboxyl group, a hydroxyl group, a carbonyl group present on the surface of the carbon black, and heating at 50 to 380 degrees, or a water-organic solvent mixture system or water The resin coating carbon black etc. which were obtained by disperse | distributing an ethylenic monomer to a surfactant mixed system and radical polymerization or radical copolymerization in presence of a polymerization initiator are mentioned. Since the resin-coated carbon black has lower conductivity than carbon black without resin coating, when used as a color filter such as a liquid crystal display, leakage of electric current is small and a low power consumption display with high reliability can be formed.

Moreover, you may add an organic pigment as an auxiliary pigment to said inorganic pigment as a light shielding material. The following effects are acquired by selecting and adding an organic pigment suitably which shows the complementary color of an inorganic pigment. For example, carbon black has a reddish black color. Therefore, by adding the organic pigment which shows blue which is a red complementary color to carbon black as an auxiliary pigment, the red group of carbon black disappears and it shows more preferable black as a whole.

As for the organic pigment in a light-shielding material, it is preferable to use an organic pigment in the range of 10-80 mass parts with respect to a total of 100 mass parts of an inorganic pigment and an organic pigment, More preferably, it is 20-60 mass parts, Most preferably, it is 20-40 mass parts of organic pigments.

As the inorganic pigment and the organic pigment, a solution obtained by dispersing the pigment at an appropriate concentration using a dispersant can be used. For example, as an inorganic pigment, the Mikuni pigment | dye carbon dispersion CF black (containing 20% of carbon concentration), the Mikuni pigment | dye carbon dispersion CF black (containing 24% of high resistance carbon), the Mikuni pigment | dye titanium black dispersion CF black ( 20% of black titanium pigment). Moreover, as an organic pigment, the Mikuni pigment | dye blue pigment dispersion CF blue (containing 20% of blue pigment), the Mikuni pigment | dye violet dispersion liquid (containing 10% of violet pigment), etc. are mentioned, for example.

Moreover, as a dispersing agent, the polymer dispersing agent of a polyethyleneimine system, a urethane resin system, and an acrylic resin system is used preferably.

When it contains a coloring material, it is preferable to contain a coloring material in the range of 1-70 mass parts in 100 mass parts of solid content, and, as for the photosensitive composition which concerns on this invention, it is more preferable to contain in the range of 20-60 mass parts.

By making a coloring material 1 mass part or more in 100 mass parts of said totals, the coloring performance of the coloring pattern formed can be improved.

On the other hand, by making the composition ratio of a coloring material into 70 mass parts or less, it can suppress that hardening hardening arises when irradiating the light ray of a predetermined wavelength.

Moreover, when using a light shielding material especially as a coloring material, it is preferable to adjust so that OD (Optical_Density) value per 1 micrometer of film thickness of the film formed may be 3.5 or more, Preferably it is 4.0 or more. When the OD value per film thickness of 1 μm is 3.5 or more, sufficient display contrast can be obtained when used for the black matrix of the liquid crystal display, and the required performance is obtained. As this light-shielding agent, carbon black is preferable.

Especially in the photosensitive composition of this invention, since the compound represented by said (1) is used as a photoinitiator even when a light shielding agent is used, high sensitivity can be acquired compared with the former.

Moreover, the photosensitive composition of this invention may contain a polymeric binder as a binder. What is necessary is just to select this polymer binder suitably according to the improvement objectives, such as compatibility, film formation property, developability, and adhesiveness.

Specifically as the polymer binder, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate , n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylamide Late, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, A monomer selected from styrene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, etc. Obtained by combining with an acidic cellulose modified product having a carboxyl group in its side chain, polyethylene oxide, polyvinylpyrrolidone, acrylonitrile, vinyl chloride, copolymer of vinylidene chloride, vinylidene chloride, chlorinated polyolefin, or vinyl chloride Copolymer of vinyl acetate, polyvinyl acetate, copolymer of acrylonitrile and styrene, copolymer of acrylonitrile and styrene, butadiene, polyvinyl alkyl ether, polyvinyl alkyl ketone, polystyrene, polyamide, polyurethane, polyethylene tere Phthalate isophthalate, acetyl cellulose, polyvinyl butyral, etc. are mentioned. In order to improve developability in especially alkaline aqueous solution, it is good to use the monomer which has carboxyl groups, such as acrylic acid and methacrylic acid, as a copolymerization component. As for said acrylic acid, methacrylic acid, the range of 5-40 mass% is preferable in a copolymerization component. Moreover, the cellulose resin which made polybasic acid anhydride react with the hydroxyl group of carboxymethylcellulose, carboxyethyl cellulose, carboxypropyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can also be used preferably.

Moreover, the photosensitive composition which concerns on this invention may add a solvent for dilution, a thermal polymerization inhibitor, an antifoamer, surfactant, etc.

Here, as a solvent which can be added to the photosensitive composition, benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene Glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene Glycoldiethyl ether, 3-methoxybutyl acetate (MA), 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether propionate Methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, and the like. have. Among them, 3-methoxybutyl acetate is preferable because it shows excellent solubility with respect to a photopolymerizable compound and a photoinitiator, and makes dispersibility of insoluble components, such as a coloring material, favorable. It is preferable that it is the quantity adjusted so that the said solvent may be 1-50 mass% in concentration of solid content, and it is more preferable that it is an quantity adjusted so that it may become 5-30 mass%.

Moreover, as a thermal polymerization inhibitor, conventionally well-known things, such as anionic, cationic, and nonionic, can be added as surfactant, such as a silicone type and a fluorine-type compound, such as hydroquinone and hydroquinone monoethyl ether.

Moreover, when forming a pattern using the photosensitive resin composition concerning this invention, a film is formed by apply | coating and drying the photosensitive resin composition concerning this invention on a board | substrate as mentioned later. In order to improve the applicability at this time and to improve the physical properties after photocuring, a polymer binder may be further contained as a binder in addition to the above components. The binder may be appropriately selected depending on the purpose of improvement such as compatibility, film formability, developability, adhesiveness, and the like.

As a manufacturing method of the photosensitive resin composition which concerns on this invention, it is obtained by mixing each above-mentioned component with a stirrer. Moreover, you may filter using a filter so that the obtained mixture may be uniform.

[Formation method]

Hereinafter, the method of forming a pattern using the photosensitive resin composition concerning this invention is demonstrated.

First, the photosensitive resin composition is applied onto a substrate by a contact transfer type coating device such as a roll coater, reverse coater, bar coater, spinner (rotary coating device), curtain flow coater ( It is applied by using a non-contact type coating device such as curtain flow coater).

After apply | coating this photosensitive resin composition, it dries and removes a solvent. The drying method is not particularly limited, and for example, (1) a method of drying for 60 seconds to 120 seconds at a temperature of 80 ° C to 120 ° C, preferably 90 ° C to 100 ° C with a hot plate, (2) You may use the method of leaving for several hours to several days at room temperature, (3) the method of removing a solvent by putting in a warm air heater or an infrared heater for several tens of minutes or several hours.

Next, through a negative mask, active energy rays, such as an ultraviolet-ray and an excimer laser light, are irradiated and partially exposed. Although the energy dose to irradiate changes with the composition of the photosensitive resin composition, about 30 mJ / cm <^2> -2000mJ / cm <^2> is preferable, for example.

Next, the film | membrane after exposure is developed with a developing solution, and patterning is carried out in a desired shape. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. Examples of the developer include organic solvents such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Next, a pattern is formed by postbake the pattern after development at about 200 degreeC. Moreover, it is preferable to expose the formed pattern to the whole surface.

The formed pattern can also be used as a spacer, a black matrix, a color filter, and an ink jet partition.

Example

Next, the Example of the photosensitive composition concerning this invention is described.

<Photopolymerizable compound>

(Resin synthesis example 1)

Resin 1 was synthesized as a photopolymerizable compound having an ethylenically unsaturated bond.

First, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and acrylic acid in a 500 ml four-necked flask 72.0 g was added, and it melt | dissolved at 90-100 degreeC, blowing air into this at a rate of 25 ml / min. Subsequently, the solution was gradually warmed to a cloudy state, heated to 120 ° C, and completely dissolved. The solution gradually became a clear viscous solution, but stirring continued as it was. The acid value was measured during this time, and heating and stirring were continued until it became less than 1.0 mg KOH / g. It took 12 hours to reach the goal. Then, it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by solid formula (a4) as colorless and transparent.

Next, 600 g of 3-methoxybutyl acetate is added to and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed. It heated up gradually and made it react at 110-115 degreeC for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1, 2, 3, 6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain Resin 1. Disappearance of the acid anhydride group was confirmed by IR spectrum.

This resin 1 is corresponded to the compound shown by Formula (a1). In addition, this resin 1 was adjusted to 50 mass% of solid content concentration with 3-methoxybutyl acetate.

(Resin synthesis example 2)

400 g, 4 g of triphenylphosphines, 153 g of acrylic acid, and 600 g of 3-methoxybutyl acetate were mixed with Epicoat YX4000H (manufactured by Japan Epoxy Resin Co., Ltd.) and reacted at 90 to 100 ° C. Then, Resin 2 was obtained by adding 40 g of 1, 2, 3, 6- tetrahydro phthalic anhydride and 360 g of biphenyl tetracarboxylic dianhydrides as a polybasic acid anhydride, and also making it react. This resin 2 had a mass average molecular weight of 7000 as measured by GPC, and an acid value of 90 mg KOH / g.

This resin 2 is corresponded to the compound shown by Formula (a1). In addition, this resin 2 was adjusted to 50 mass% of solid content concentration with 3-methoxybutyl acetate.

(Resin synthesis example 3)

　Resin 3 was synthesize | combined similarly except having used 500 g of dicyclopentadiene type epoxy resins (epoxy equivalent 283) represented by following formula (a5) instead of epicoat YX4000H in resin synthesis example 2. The molecular weight of this resin 3 was 4500. In addition, this resin 3 was adjusted to 50 mass% of solid content concentration with 3-methoxybutyl acetate.

<Photoinitiator>

In Formula (1), what the group of A, B, G, E shows in Table 1 was used.

(Example, Comparative Example)

About the photosensitive composition which concerns on a present Example and a comparative example, it prepared by the composition shown in Table 2. In addition, the solvent was adjusted so that 3-methoxybutyl acetate: cyclohexanone = 70: 30 (mass ratio) and solid content concentration of the photosensitive composition might be 18 mass%. The mixture of this composition was mixed with the stirrer for 2 hours, and it filtered with the 5 micrometer membrane filter, and obtained the photosensitive composition.

* 1 25 mass% carbon black, a solvent: 3-methoxybutyl acetate, the Mikuni dye company

* 2 Each resin used what was adjusted so that it might become 50% of solid content as shown in the resin synthesis example.

* 3 dipentaerythritol hexaacrylate

* 4 pentaerythritol tetraacrylate

The obtained photosensitive composition was applied onto a glass substrate having a clean surface having a thickness of 1 mm using a spin coater (TR25000: manufactured by Tokyooka Co., Ltd.) so as to have a dry film thickness of 1.2 μm, and at 90 ° C. for 2 minutes. It dried and formed the film | membrane (photosensitive layer) of the photosensitive composition. Next, this film was selectively irradiated with ultraviolet rays through a negative mask. Thereafter, a black matrix pattern including a line having a line width of 20 μm was formed by spray development at 25 ° C. for 60 seconds with an aqueous 0.5 mass% sodium carbonate solution. Thereafter, postbake was performed in a 220 ° C.-30 min circulating oven. The film thickness of each produced black matrix was 1.0 μm.

Moreover, about each produced black matrix, when it measured with OD measuring apparatus D-200II (made by Gretagmark-Bess company), OD value was 4.0.

Table 3 shows the results of evaluation (pattern straightness, peeling, residue) of the black matrix pattern of each of the above-mentioned Examples and Comparative Examples obtained as described above.

In addition, the exposure was increased in steps of 5 mJ up to 10 to 180 mJ / cm ² for sensitivity evaluation, and development was carried out under the above conditions. Moreover, as "Bias + 1.0 micrometer", the exposure amount which the line | wire width of the black mask pattern formed with respect to a 20 micrometer mask becomes 20 micrometer + 1 micrometer was evaluated. Since the photosensitive composition in the present invention is a negative type resist, the larger the exposure amount, the larger the CD (Critical Dimension). Usually, the line width for mass production purposes is mask line width + 1-2 micrometers. When the patterning can be performed at a lower exposure amount, the exposure time can be shortened, thereby improving the throughput of the line.

As a result of the determination, even though the pattern obtained in the Example had an OD value of 4.0 and the light shielding property was high, the linearity was excellent even when the exposure amount was 65 mJ / cm ² , and no peeling off of the residue or the substrate was confirmed. On the other hand, in each comparative example, there existed many pattern peelings in the low exposure amount, and the straightness was also not good. In the comparative example, the value of Bias + 1 μm was undesirable because the line width became thinner than the target value when the exposure amount was smaller than 95 mJ / cm ² .

Claims (10)

In the photosensitive composition containing a photopolymerizable compound and a photoinitiator, The said photoinitiator has a skeleton represented by Formula (1), and contains the compound whose absorbance in 365 nm is 0.3 or more.

(In Formula (1), A, B, and G are monovalent organic groups, and E is a conjugated double-bonding cyclic group which may have a substituent and is a 5-membered ring group having N atoms in the ring.) The method of claim 1, The bond length of the N atom represented by (alpha) and the O atom represented by (beta) in said Formula (1) is 1.360 kPa or more, The photosensitive composition characterized by the above-mentioned. delete delete delete The method of claim 1, E has a N atom in the substituent of the conjugated double bond cyclic group. The method of claim 6, The substituent is a photosensitive composition, characterized in that N atoms are bonded directly to the conjugated double bond cyclic group. The method of claim 7, wherein The substituent is —NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ each independently represents an alkyl group and an alkoxy group, which may be substituted with a halogen atom, and among these, the alkylene moiety of the alkyl group and the alkoxy group may be an ether bond or a thioether). The photosensitive composition may be interrupted by a bond or an ester bond, and R ⁴ and R ⁵ may form a ring as one. The method of claim 1, A photosensitive composition comprising a coloring material. 10. The method of claim 9, The coloring material is a light-sensitive material, characterized in that the light-shielding material.